Sensing the framework state and guest molecules in MIL-53(Al) via the electron paramagnetic resonance spectrum of VIV dopant ionsElectronic supplementary information (ESI) available: X-Ray powder diffraction patterns and N2 adsorption isotherms of reported samples, available lattice parameters for three states in MIL-53(Al) and MIL-53(Ga), hydration of np-d followed in situ with EPR spectroscopy, simulation of activated V-doped MIL-53(Al) in np-h state with two components, superhyperfine interac

X-ray diffraction (XRD) and electron paramagnetic resonance spectroscopy (EPR) were combined to study the structural transformations induced by temperature, pressure and air humidity of the "breathing" metal-organic framework (MOF) MIL-53(Al), doped with paramagnetic V IV ions, after activation. The correlation between in situ XRD and thermogravimetric analysis measurements showed that upon heating this MOF in air, starting from ambient temperature and pressure, the narrow pore framework first dehydrates and after that makes the transition to a large pore state ( lp ). The EPR spectra of V IV &z.dbd;O molecular ions, replacing Al-OH in the structure, also allow to distinguish the as synthesized, hydrated ( np-h ) and dehydrated narrow pore ( np-d ), and lp states of MIL-53(Al). A careful analysis of EPR spectra recorded at microwave frequencies between 9.5 and 275 GHz demonstrates that all V IV &z.dbd;O in the np-d and lp states are equivalent, whereas in the np-h state (at least two) slightly different V IV &z.dbd;O sites exist. Moreover, the lp MIL-53(Al) framework is accessible to oxygen, leading to a notable broadening of the V IV &z.dbd;O EPR spectrum at pressures of a few mbar, while such effect is absent for the np-h and np-d states for pressures up to 1 bar. The EPR spectrum of V IV dopant ions was used to discriminate different states of MIL-53(Al) and to detect oxygen gas.